Films for optical use and methods of making such films

ABSTRACT

Films for optical use, articles containing such films, methods for making such films, and systems that utilize such films, are disclosed

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority under 35 U.S.C. §119 to U.S.Provisional Patent Application Ser. No. 60/544,089, entitled “ATOMICLAYER DEPOSITION FOR HIGH QUALITY OPTICAL COATINGS,” and filed on Feb.12, 2004, the entire contents of which are hereby incorporated byreference.

TECHNICAL FIELD

This invention relates to films for optical use, articles containingsuch films, methods for making such films, and systems that utilize suchfilms.

BACKGROUND

Optical devices and optical systems are commonly used where manipulationof light is desired. Examples of optical devices include lenses,polarizers, optical filters, antireflection films, retarders (e.g.,quarter-waveplates), and beam splitters (e.g., polarizing andnon-polarizing beam splitters).

SUMMARY

This invention relates to films for optical use, articles containingsuch films, methods for making such films, and systems that utilize suchfilms.

In one aspect, the invention features a method for forming film on asubstrate, including forming a layer of a first material by sequentiallydepositing a plurality of monolayers of the first material, one of themonolayers of the first material being deposited on a first surface ofthe substrate, wherein the film includes the layer of the first materialand the substrate includes a polymer.

In another aspect, the invention features a method for forming amultilayer film on an optical component, including forming a layer of afirst material by sequentially depositing a plurality of monolayers ofthe first material, one of the monolayers of the first material beingdeposited on a first surface of the optical component, and forming alayer of a second material by sequentially depositing a plurality ofmonolayers of the second material, one of the monolayers of the secondmaterial being deposited on a surface of the layer of the firstmaterial, wherein the multilayer film includes the layers of the firstmaterial and second material and the optical component is a lens.

In another aspect, the invention features a method, including usingatomic layer deposition to simultaneously deposit a film on first andsecond surfaces of a substrate, the first surface being opposite thesecond surface.

In another aspect, the invention features a method, including usingatomic layer deposition to simultaneously deposit a layer of a firstmaterial on first and second surfaces of an optical substrate, the firstsurface being opposite the second surface.

In another aspect, the invention features a method, including usingatomic layer deposition to deposit a multilayer film on a surface of asubstrate comprising a polymer.

In another aspect, the invention features a method for forming a film ona substrate, including forming a layer of a first material bysequentially depositing a plurality of monolayers of the first material,one of the monolayers of the first material being deposited on a firstsurface of the substrate, wherein the film comprises the layer of thefirst material and the substrate comprises a lens.

In another aspect, the invention features a method for forming a film ona substrate comprising a curved surface, including forming a layer of afirst material by sequentially depositing a plurality of monolayers ofthe first material, one of the monolayers of the first material beingdeposited on the curved surface of the substrate, wherein the filmcomprises the layer of the first material.

In another aspect, the invention features a method for forming a film ona substrate, including forming a layer of a first material bysequentially depositing a plurality of monolayers of the first material,one of the monolayers of the first material being simultaneouslydeposited on first and second surfaces of the substrate, wherein thefilm comprises the layer of the first material and the first surface isopposite the second surface.

In another aspect, the invention features a method for forming a film ona substrate, including forming a layer of a first material bysequentially depositing a plurality of monolayers of the first material,one of the monolayers of the first material being simultaneouslydeposited on first and second non-coplanar surfaces of the substrate,wherein the film comprises the layer of the first material and the firstsurface is contiguous with the second surface.

In another aspect, the invention features a method, including usingatomic layer deposition to deposit a multilayer film on a surface of alens.

In another aspect, the invention features a method, including usingatomic layer deposition to deposit a multilayer film on a curved orstructured surface.

Embodiments can include one or more of the following features.

Depositing the plurality of monolayers of the first material can includedepositing a monolayer of a precursor and exposing the monolayer of theprecursor to a reagent to provide a monolayer of the first material. Thereagent can chemically react with the precursor to form the firstmaterial. For example, the reagent can oxidize the precursor to form thefirst material. Depositing the monolayer of the precursor can includeintroducing a first gas comprising the precursor into a chamber housingthe substrate. A pressure of the first gas in the chamber can be about0.01 to about 100 Torr. Exposing the monolayer of the precursor to thereagent can include introducing a second gas comprising the reagent intothe chamber. A pressure of the second gas in the chamber can be about0.01 to about 100 Torr. A third gas can be introduced into the chamberafter the first gas is introduced and prior to introducing the secondgas. The third gas can be inert with respect to the precursor. The thirdgas can include at least one gas selected from the group consisting ofhelium, argon, nitrogen, neon, krypton, and xenon. The precursor can beselected from the group consisting of tris(tert-butoxy)silanol,(CH₃)₃Al, TiCl₄, SiCl₄, SiH₂Cl₂, TaCl₃, AlCl₃, Hf-ethaoxide andTa-ethaoxide. The first material can be a dielectric material.

The methods can include forming a layer of a second material bysequentially depositing a plurality of monolayers of the secondmaterial, one of the monolayers of the second material being depositedon the layer of the first material, wherein the second material isdifferent from the first material and the film comprises the layer ofthe second material. Depositing the plurality of monolayers of thesecond material can include depositing a monolayer of a precursor andexposing the monolayer of the precursor to a reagent to provide amonolayer of the second material. The reagent can chemically react withthe precursor to form the second material. For example, the reagent canoxidize the precursor to form the second material. Depositing themonolayer of the precursor can include introducing a first gascomprising the precursor into a chamber housing the substrate. Apressure of the first gas in the chamber can be about 0.01 to about 100Torr. Exposing the monolayer of the precursor to the reagent can includeintroducing a second gas comprising the reagent into the chamber. Apressure of the second gas in the chamber can be about 0.01 to about 100Torr. The chamber can be purged with a purge gas after the first gas isintroduced and prior to introducing the second gas. The purge gas can beinert with respect to the first precursor. The purge gas can include atleast one gas selected from the group consisting of helium, argon,nitrogen, neon, krypton, and xenon. The precursor can be selected fromthe group consisting of tris(tert-butoxy)silanol, (CH₃)₃Al, TiCl₄,SiCl₄, SiH₂Cl₂, TaCl₃, AlCl₃, Hf-ethaoxide and Ta-ethaoxide. The secondmaterial can be a dielectric material.

The methods can further include forming a layer of a third material on asurface of the layer of the second material, wherein the third materialis different from the second material and the film includes the layer ofthe third material. The third material can be the same as the firstmaterial. The layer of the third material can be deposited using atomiclayer deposition. The method can also include forming a layer of afourth material on a surface of the layer of the third material, whereinthe fourth material is different from the third material and the filmincludes the layer of the fourth material. The fourth material can bethe same as the second material. The layer of the fourth material can bedeposited using atomic layer deposition. The methods can include formingadditional layers that are supported by the layer of the fourthmaterial. The additional layers can be formed using atomic layerdeposition.

The substrate can be an optical component. The methods can includeforming a layer of the first material on a second surface of thesubstrate simultaneously to forming the layer of the first material onthe first surface, wherein the second surface is opposite or contiguouswith the first surface. The layer of the first material can be formed onthe second surface by sequentially depositing a plurality of monolayersof the first material, one of the monolayers of the first material beingdeposited on the second surface of the substrate.

The methods can include forming a layer of the second material on alayer of the first material deposited on a second surface of thesubstrate simultaneously to forming the layer of the second material onthe layer of the first material on the first surface, wherein the secondsurface is opposite or contiguous with the first surface. The layer ofthe second material can be formed on the layer of the first materialdeposited on the second surface by sequentially depositing a pluralityof monolayers of the second material, one of the monolayers of thesecond material being deposited on a surface of the layer of the firstmaterial deposited on the second surface.

While forming the layer of the first material, the substrate can have atemperature of about 500° C. or less (e.g., about 300° C. or less, about200° C. or less, about 150° C. or less, about 100° C. or less, about 80°C. or less, about 70° C. or less, about 60° C. or less, about 50° C. orless).

In embodiments where the substrate includes a polymer, the polymer canbe a thermoset polymer or a thermoplastic polymer.

In a further aspect, the invention features an article, including asubstrate having a first surface and a second surface contiguous withthe first surface, the first and second surfaces being non-coplanar, afirst multilayer film disposed on the first surface, and a secondmultilayer film disposed on the second surface, wherein the secondmultilayer film is contiguous with the first multilayer film.

In another aspect, the invention features an article, including anoptical component having a first surface and a second surface oppositethe first surface, a layer of a first material disposed on the firstsurface, and a layer of the first material disposed on the secondsurface, wherein a perpendicular optical thickness of the layer of thefirst material at a location on the first surface is within about fivepercent of a perpendicular optical thickness of the layer of the firstmaterial on a corresponding location on the second surface.

In another aspect, the invention features an article, including asubstrate having a surface that has a radius of curvature of about 10meters or less, wherein the surface has a first location and a secondlocation and an angle between a surface normal at the first and secondlocations is about two degrees or more; and a film disposed on thesurface, wherein the film includes a layer of a first material and aperpendicular optical thickness of the layer at the first location iswithin about one percent of a perpendicular optical thickness of thelayer at the second location.

In another aspect, the invention features an article, including asubstrate having a first surface and a second surface opposite the firstsurface, a first film disposed on the first surface, and a second filmdisposed on the second surface, wherein a perpendicular opticalthickness of the first film at a location on the first surface is withinabout five percent of a perpendicular optical thickness of the secondfilm at a corresponding location on the second surface.

In another aspect, the invention features an article, including asubstrate comprising a polymer, and a multilayer film disposed on afirst surface of the substrate.

In another aspect, the invention features an optical filter, including amultilayer film defining an optical axis, wherein the optical filtertransmits 50% of light having a wavelength λ_(i) propagating along theoptical axis, and the optical filter transmits 50% of light having awavelength λ₂ incident on the multilayer film at an angle of 30 degreeswith respect to the optical axis, wherein |λ₁−λ₂| is about 30 nm orless.

Embodiments may include one or more of the following features.

The first and second multilayer films can include a contiguous layer ofa first material. The first and second multilayer films can include acontiguous layer of a second material, wherein the second material isdifferent from the first material and the contiguous layer of the secondmaterial is supported by the contiguous layer of the first material. Thefirst and second multilayer films can include three or more contiguouslayers, wherein adjacent layers are formed from different materials.

The substrate can be an optical component (e.g., a lens, such as aFresnel lens, an optical flat). The substrate can include a glass. Theglass can be selected from the group consisting of borosilicate glass,glass-ceramic, quartz, fused silica, and soda-lime glass. Alternatively,or additionally, the substrate can include a polymer (e.g., a thermosetpolymer or a thermoplastic polymer). The polymer can be selected fromthe group consisting of polycarbonate, acrylic, polyester, polyethylene,polypropylene, polyvinylchloride, and polymethylemethacrylate. Thesubstrate can include a material that has a glass transition temperatureof about 250° C. or less (e.g., about 200° C. or less, about 150° C. orless, about 100° C. or less, about 80° C. or less). The substrate caninclude a substrate material having a coefficient of thermal expansionwithin ten percent of a coefficient of thermal expansion of the firstmaterial for temperatures between about 0° C. and 300° C. The surfacecan have a radius of curvature of about 100 meters or less.Alternatively, the surface can be substantially planar. The surface canbe a structured surface. The first material can be a dielectricmaterial. The first material can be an oxide. For example, the oxide canbe a metal oxide. In some embodiments, the metal oxide is selected fromthe group consisting of SiO₂, Al₂O₃, Nb2O₅, TiO₂, ZrO₂, HfO₂ and Ta₂O₅.

The contiguous layer can have a perpendicular optical thickness of about1 nm or more (e.g., about 10 nm or more, about 20 nm or more). In someembodiments, the contiguous layer can have a perpendicular opticalthickness of about 5,000 nm or less (e.g., about 1,000 nm or less, about500 nm or less).

The first and second multilayer films are antireflection films. In someembodiments, the article is an optical filter. The optical filter can bean infrared filter. The infrared filter can reduce transmission of lighthaving wavelengths from about 650 nm to about 1,100 nm through thearticle. The optical filter can be an ultraviolet filter. Theultraviolet filter can reduce transmission of light having wavelengthsfrom less than about 400 nm through the article.

A refractive index of the first material can be different from arefractive index of the second material. A perpendicular opticalthickness of the contiguous layer of the first material can be the sameas a perpendicular optical thickness of the contiguous layer of thesecond material. Alternatively, a perpendicular optical thickness of thecontiguous layer of the first material can be different from aperpendicular optical thickness of the contiguous layer of the secondmaterial. The article can include a third multilayer film disposed on athird surface of the substrate, the third surface being opposite thefirst surface. The first, second, and third multilayer films can beidentical.

In some embodiments, λ₁ is about 650 mn.

In a further aspect, the invention features an optical system, includinga lens for imaging light from an object to an image plane, and anoptical filter comprising a plurality of layers positioned relative tothe lens to reduce an amount of focused light of a wavelength λ by about20 percent or more at the image plane relative to an identical opticalsystem without the optical filter, wherein one of the layers is disposedon a first surface of the lens.

In another aspect, the invention features an optical system, includingan optical filter positioned relative a lens and an image plane, whereinthe optical filter includes a substrate having first and secondsurfaces, wherein the first surface is opposite the second surface, anda first and second multilayer film disposed on the first and secondsurfaces, respectively, wherein the first multilayer film is identicalto the second multilayer film.

In another aspect, the invention features a digital camera including oneof the optical systems.

In a further aspect, the invention features a cell phone including thedigital camera.

Embodiments can include one or more of the following features.

The first surface can have a radius of curvature of about two meters orless. The image plane can be about 5 cm or less from the lens (e.g.,about 1 cm or less, about 0.5 cm or less). The optical systems caninclude a detector positioned at the image plane. The detector can be acharge coupled device (CCD) array or complementary metal oxidesemiconductor (CMOS) array. The optical filter can be disposed on asurface of the detector.

The plurality of layers can include a plurality of dielectric layers.Alternating layers of the plurality of layers can have differentrefractive indices. The plurality of layers can include a layer disposedon a second surface of the lens opposite the first surface. λ can beabout 650 nm or more. For example, λ can be between about 650 nm and1,100 nm. The optical filter can reduce focused light of wavelength λ byabout 50 percent or more at the image plane (e.g., about 80 percent ormore, about 90 percent or more, about 95 percent or more).

The optical systems can include a second lens for imaging light from theobject to the image plane. One of the layers of the optical filter canbe disposed on a surface of the second lens. Rays of imaged light canhave a maximum divergence of about 20 degrees or less at the firstsurface (e.g., about 15 degrees or less, about 10 degrees or less). Theoptical filter can be positioned between the lens and the image plane.

Embodiments of the invention may include one or more of the followingadvantages.

In some embodiments, the film can include one or more layers that arehighly uniform (e.g., highly uniform thickness, highly uniformrefractive index), which can, for example, result in a film which itselfis highly uniform (e.g., highly uniform thickness, highly uniformrefractive index). An article, such as an optical device, containing oneor more such films can exhibit enhanced performance. As an example, anoptical filter containing one or more such films can be highly effectiveat blocking undesired wavelengths while also being highly effective attransmitting desired wavelengths.

Highly uniform layers can be repeatably deposited from deposition todeposition, providing multilayer films which are highly uniform (e.g.,highly uniform thickness, highly uniform refractive index) and providingfilms on different substrates which have layers that are highly uniform(e.g., highly uniform thickness, highly uniform refractive index).Articles, such as optical devices, containing such films canbe-manufactured to conform to tight uniformity specifications. As anexample, optical filters containing such films can perform withinstringent optical performance specifications. For example, the positionof a transmission band edge for a batch of optical filters containingsuch films can be substantially the same for each filter.

In certain embodiments, a film can include one or more layers that areconformal layers supported by a substrate. The conformal layer(s) canalso be highly uniform (e.g., have highly uniform thickness). Anarticle, such as an optical device, having containing one or moreoptical such films can exhibit enhanced performance. As an example, astructured surface of a Fresnel lens can be coated with anantireflection (AR) film, providing enhanced performance of the lens. AnAR film on such a lens can reduce “ghosting,” which can occur due tounwanted reflections at the structured surface of the lens. As anotherexample, a highly uniform film (e.g., highly uniform thickness, highlyuniform refractive index) can be deposited on a curved surface, such ason the surface of a ball lens or the inner surface of an integratingsphere.

In some embodiments, the methods can allow for multiple (e.g., opposite)surfaces of a substrate to be deposited at the same time. This canreduce the cost and/or complexity associated with depositing the films.This can also allow for multiple, substantially identical films to beformed on different surfaces of the substrate, reduce deposition time,and/or reduce excessive handling of a substrate. An article, such anoptical device, formed using such a method can meet tight opticalspecifications. As an example, an AR film can be coated onto multiplesurfaces of a substrate (e.g., a lens, a prism, or an optical flat)during a single deposition run.

In certain embodiments, the methods can be used to partially or fullyencapsulate a substrate. This can be advantageous, for example, when itis desirable to protect the substrate from its environment (e.g., whenexposing the substrate to the environment could be detrimental to theperformance characteristics of the substrate).

In some embodiments, the methods are compatible with thermally unstablesubstrates (e.g., polymer substrate with glass transition temperaturesof about 300° or less).

In certain embodiments, the methods can be used to form integratedoptical components (e.g., a lens that also serves as the substrate forone or more films, such as films that form an optical filter). Suchintegrated components can be used to reduce the number of discretecomponents present in an optical system designed for a particularpurpose. This can, for example, reduce the size, cost and/or complexityof an optical system.

Other features, and advantages of the invention will be apparent fromthe description and drawings, and from the claims.

DESCRIPTION OF DRAWINGS

FIG. 1A is a cross-sectional view of an optical filter.

FIG. 1B is a cross-sectional view of a portion of the optical filtershown in FIG. 1A.

FIG. 1C is a plot of a transmission spectrum for an optical filtershowing transmission for on-axis and off-axis incidence.

FIG. 2A is a schematic diagram of an atomic layer deposition system.

FIG. 2B is a flow-chart summarizing an atomic layer deposition process.

FIG. 3 is a cross-sectional view of contiguous multilayer filmsdeposited on contiguous surfaces of a substrate.

FIG. 4 is a cross-sectional view of a lens with films on opposingsurfaces.

FIG. 5 is a cross-sectional view of a portion of a Fresnel lens with afilm on the structured surface.

FIG. 6 is a schematic view of an imaging system including an opticalfilter.

FIG. 7 is a schematic view of another imaging system including anoptical filter.

FIG. 8 is a schematic view of a further imaging system including anoptical filter.

FIG. 9 is a schematic view of another imaging system including anoptical filter.

FIG. 10 is a transmission spectrum of an optical filter for lightincident at 0° and 30°.

FIG. 11 is a transmission spectrum of another optical filter for lightincident at 0°.

Like reference symbols in the various drawings indicate like elements.

DETAILED DESCRIPTION

Referring to FIG. 1A, an optical filter 10 is composed of two multilayerfilms 11 and 12, disposed on opposite surfaces 21 and 22 of a substrate20 (e.g., a glass optical flat). Optical filter 10 substantiallyreflects light of certain wavelengths impinging on the filterpropagating along an axis 50, and substantially transmits light of otherwavelengths. Optical filter 10 also reflects light of certainwavelengths impinging on the filter at an angle to axis 50, whiletransmitting light of other wavelengths. Both multilayer films 11 and 12include a number alternating high refractive index and low refractiveindex layers formed from dielectric materials.

The structure of multilayer film 11 is shown in FIG. 1B. Multilayer film11 is composed of seven high index layers 30 and seven low index layers32. The composition and structure of multilayer film 12 is the same asmultilayer film 11. In other words, both multilayer films include thesame number of dielectric layers, and the composition and thickness ofcorresponding layers in the films is the same. As used herein,corresponding layers refer to layers in multilayer films 11 and 12 thatare in the same relative position within the multilayer film.

The thickness and composition of each layer in multilayer films 11 and12 depend on the desired spectral characteristics of optical filter 10.In some cases, the thickness of each layer is about 0.25 λ/n where λ isa wavelength to be reflected by the filter and n is the refractive indexof the layer. Of course, the thickness of a given layer will varydepending on the refractive index of the material used to form thelayer.

In some embodiments, the thickness of each layer can be determined usingan algorithm that optimizes the layer thickness based on the desiredoptical properties of the optical filter. For example, where maximumreflectance across a certain portion of the spectrum is desired, thealgorithm can determine reflectance of the filter for differentcombinations of layers thickness to converge onto a structure in whichthe reflectance is highest. Examples of commercially available softwarethat can be used to perform such calculations are FilmWizard™, which isavailable from Scientific Computing International (Carlsbad, Calif.),and TFCalc, available from Software Spectra, Inc. (Portland, Oreg.).

As used herein, the perpendicular thickness of a portion of a layerrefers to the thickness of the portion of the layer in a directionnormal to the portion of the substrate surface closest to the portion ofthe layer. Generally, layer thickness (e.g., perpendicular layerthickness) can be determined by studying a cross section of the layerusing electron microscopy, ellipsometry or by parametric fittingcomputational data to spectroscopic data.

As used herein, the perpendicular optical thickness of a portion of alayer refers to the optical thickness of the portion of the layer in adirection normal to the portion of the substrate surface closest to theportion of the layer.

As used herein, the optical thickness of a portion of a layer refers tothe product of the thickness of the portion of the layer and therefractive index of the portion. Where the portion of the layer isoptically inhomogeneous (i.e., the refractive index varies through thelayer along the direction in which the thickness is measured), theoptical thickness refers to the refractive index integrated with respectto the thickness. For an optically homogeneous layer, this integralreduces to the previous definition.

In each multilayer film, the perpendicular optical thickness of eachlayer can be the same as or different than other layers. For example, inembodiments where optical filter 10 is designed to reflect a narrow bandof wavelengths (e.g., about 10 mn), the perpendicular optical thicknessof each layer can be 0.25 λ₀, where λ₀ is the central wavelength in thereflection band. Alternatively, where optical filter 10 is designed toreflect a broad band of wavelengths (e.g., about 100 mn or more, about150 nm or more, about 200 nm or more), the perpendicular opticalthickness of layers can vary. In this example, different groups oflayers in each multilayer film can have a perpendicular opticalthickness equal to 0.25 λ_(i) for different wavelengths, λ_(i), withinthe desired reflection band. In some embodiments, the perpendicularoptical thickness of each layer can be in the range of about 20 nm toabout 1,000 nm. For example, the perpendicular optical thickness of eachlayer can be about 50 nm or more (e.g., about 100 nm or more, about 150nm or more, about 200 nm or more, about 250 nm or more, about 300 nm ormore). In embodiments, the perpendicular optical thickness of the layerscan be about 800 nm or less (e.g., about 600 nm or less, about 500 mn orless).

In general, the perpendicular thickness of each layer in a multilayerfilm can be substantially uniform. For example, the perpendicularthickness of a given layer can vary by about 2% or less betweendifferent portions of a layer (e.g., about 1% or less, about 0.5% orless, about 0.2% or less, about 0.1% or less, about 0.05% or less, about0.02% or less, about 0.01% or less, 0.001% or less). In someembodiments, the perpendicular thickness of each layer in a multilayerfilm can vary by about 10 nm or less between different portions of thelayer (e.g., about 8 nm or less, about 5 nm or less, about 3 nm or less,about 2 nm or less, about 1 nm or less, about 0.5 nm or less).

Generally, the perpendicular optical thickness of each layer inmultilayer films 11 and 12 can be substantially uniform. In someembodiments, a layer can have a perpendicular optical thickness thatvaries by about 2% or less between different portions of the layer(e.g., about 1% or less, about 0.5% or less, about 0.2% or less, about0.1% or less, about 0.05% or less, about 0.02% or less, about 0.01% orless, 0.001% or less). The perpendicular optical thickness of one ormore deposited layers can vary by about 20 nm or less between differentportions of the layer (e.g., about 10 nm or less, about 5 nm or less,about 3 nm or less, about 2 nm or less, about 1 nm or less, about 0.5 nmor less).

As mentioned previously, the thickness and composition of correspondinglayers in multilayer films 11 and 12 are substantially the same. Forexample, the layers in each multilayer film adjacent the substratesurfaces are corresponding layers. In some embodiments, perpendicularlayer thickness of corresponding layers can vary by about 2% or less(e.g., about 1% or less, about 0.5% or less, about 0.2% or less, about0.1% or less, about 0.05% or less, about 0.02% or less, about 0.01% orless, 0.001% or less) at corresponding locations in each multilayer film(e.g., where optical axis 50 intersects each multilayer film). In someembodiments, the perpendicular thickness of one or more correspondinglayers can vary by about 10 nm or less (e.g., about 8 nm or less, about5 nm or less, about 3 nm or less, about 2 nm or less, about 1 nm orless, about 0.5 nm or less) at corresponding locations in multilayerfilm 11 and multilayer film 12.

Furthermore, the perpendicular optical thickness of corresponding layersin multilayer film 11 and multilayer film 12 can be substantiallyuniform. In some embodiments, the perpendicular optical thickness ofcorresponding layers in multilayer films can have a perpendicularoptical thickness that varies by about 2% or less between thecorresponding layers (e.g., about 1% or less, about 0.5% or less, about0.2% or less, about 0.1% or less, about 0.05% or less, about 0.02% orless, about 0.01% or less, 0.001% or less). The perpendicular opticalthickness of corresponding layers can vary by about 15 nm or less (e.g.,about 10 nm or less, about 5 nm or less, about 3 nm or less, about 2 nmor less, about 1 nm or less, about 0.5 nm or less) at correspondinglocations in multilayer film 11 and multilayer film 12.

The dielectric materials used to form layers of multilayer films 11 and12 are selected based on their optical properties (e.g., theirrefractive index at the wavelengths at which the films are to function,and their absorption at these wavelengths), their compatibility witheach other and the substrate, and their compatibility with the processused to manufacture the optical filter. In some embodiments, thedielectric materials include oxides (e.g., metal oxides, fluorides(e.g., metal fluorides), sulphides, and/or nitrides (e.g., metalnitrides). Examples of oxides include SiO₂, Al₂O₃, Nb₂O₅, TiO₂, ZrO₂,HfO₂, SnO₂, ZnO, ErO₂, Sc₂O₃, and Ta₂O₅. Examples of fluorides includeMgF₂. Other examples include ZnS, SiN_(x), AlN, TiN, and HfN.Alternatively, or additionally, the materials can include non-dielectricmaterials, such as metals (e.g., Al, Pt, Cu).

Examples of high index materials include TiO₂, which has a refractiveindex of about 2.35 at 632 nm, and Ta₂O₅, which has a refractive indexof 2.15 at 632 nm. Examples of low index materials include SiO₂ andAl₂O₃, which have refractive indices of 1.45 and 1.65 at 632 nm,respectively.

In some embodiments, the dielectric materials are substantiallyamorphous (e.g., about 95% or more, about 98% or more, about 99% or moreamorphous). Typically, an amorphous material is optically isotropic andmay transmit light better than dielectric layers that are partially ormostly crystalline. In some embodiments, however, some or all of one orboth of the dielectric materials may be crystalline.

The optical transmission characteristics of filter 10 can vary dependingon a number of design parameters, which include the number of layers ineach multilayer film, the optical thickness of each layer, the relativeoptical thickness of different layers, and the refractive index of eachlayer. In some embodiments, the filter can be designed to transmitsubstantially all light within a band of wavelengths impinging on itwithin a cone of incident angles relative to an optical axis 50, whilereflecting substantially all UV, visible, and/or IR wavelengths outsideof that band (e.g., all outside the transmission band from about 200 nmto about 2,000 nm). The wavelengths substantially transmitted by thefilter are referred to as “pass wavelengths,” while the reflectedwavelengths are referred to as “block wavelengths.” The width of theband of pass wavelengths can be relatively broad (e.g., from about 200nm to about 300 nm or more), or can be narrow (e.g., from about 0.4 nmto about 20 nm or less).

FIG. 1C shows an exemplary transmission spectrum of an optical filter.Curve C1 corresponds to the transmission of light incident on theoptical filter parallel to optical axis 50. For this example, the passwavelengths for on-axis light correspond to wavelengths between λ₁ andλ₂, which correspond to the wavelengths at which the optical filtertransmits 50% of incident light. In some embodiments, the band of passwavelengths can correspond to the visible portion of the electromagneticspectrum (e.g., from about 400 nm to about 700 nm). The blockedwavelengths can include IR wavelengths (e.g., from about 700 nm to about2,000 nm).

In some embodiments, optical filter 10 can have high transmission atsome or all of the pass wavelengths. For example, transmission at passwavelengths can be about 95% or more (e.g., about 97% or more, about 98%or more, about 99% or more, about 99.5% or more). In general, thetransmission at pass wavelengths depends on the absorption andhomogeneity of materials used to form the optical filter, and theuniformity and precision of layer thickness in the multilayer films. Forexample, materials with relatively high absorption at pass wavelengthscan reduce transmission by absorbing light impinging on the filter.Inhomogeneities (e.g., impurities and/or crystalline domains) in thefilter can reduce transmission by scattering impinging light. Layerthickness discrepancies can result in coherent reflection of impinginglight at pass wavelengths, reducing its transmission. Transmission isfurther improved by reducing reflectance losses at the interfacesbetween the optical filter and the atmosphere. In embodiments in whichmultilayer films are disposed on opposite surfaces of the substrate,they can reduce reflectance of light at transmitted wavelengths comparedwith optical filters in which only one surface is coated with amultilayer film.

Transmission at all or some of the block wavelengths can be relativelylow, such as about 5% or less (e.g., about 4% or less, about 3% or less,about 2% or less, about 1% or less). Increasing the optical filter'sreflectance and/or absorption at these wavelengths can reducetransmission at block wavelengths. Increasing the number of layers ineach multilayer film and/or increasing the difference in refractiveindex between the low index and high index layers can increasereflectance of block wavelengths.

In some embodiments, optical filter 10 can have a small blue shift inthe transmission band edge for light incident on the filter atnon-normal angles. The position of the transmission band edgecorresponds to the wavelengths at which the optical filter transmits 50%of light impinging thereon. In FIG. 1C, these correspond to wavelengthsλ_(i) and λ₂ for curve C1. These wavelengths typically vary as afunction of the incident angle of the light due to the variation inoptical thickness of layers in each multilayer film for off-axis light.The nominal position of the band edge corresponds to normally incidentlight. The band edge shifts to shorter wavelengths for increasingincident angles—hence the term “blue shift.” For example, curve C2 inFIG. 1C shows the transmission spectrum of the filter for light incidenton the filter at an angle that is non-parallel to axis 50. In thisexample, the positions of the band edges have shifted from λ₁ to λ₁′ andfrom λ₂ to λ₂′, where λ₁′<λ₁ and λ₂′<λ₂. The amplitude of the blue shiftcan be reduced by selecting materials with a relatively high refractiveindex to form the layers in optical filter 10 (e.g., refractive index ofabout 1.7 or more, about 1.8 or more, about 1.9 or more, about 2.0 ormore). In some embodiments, the blue shift can be about 30 nm or lessfor light incident at 30 degrees relative to axis 50 (e.g., about 25 nmor less, about 23 nm or less, about 20 nm or less, about 18 nm or less,about 15 nm or less).

In general, a multilayer film can be prepared as desired. In someembodiments, multilayer films 11 and 12 can be prepared using atomiclayer deposition (ALD). Referring to FIG. 2A, an ALD system 100 is usedto deposit multilayer films 11 and 12 on surfaces 21 and 22,respectively, of substrate 20. An additional multilayer film 101 isdeposited on exposed surface 102. Optionally, multilayer film 101 can beremoved from substrate 20 once the deposition process is completed, toprovide optical filter 10 (see FIG. 1A). Deposition of multilayer films11, 12, and 101 occurs monolayer by monolayer, providing substantialcontrol over the composition and thickness of the films. Duringdeposition of a monolayer, vapors of a precursor are introduced into thechamber and are adsorbed onto substrate surfaces 11, 12, and 102 orpreviously deposited layers adjacent these surfaces. Subsequently, areactant is introduced into the chamber that reacts chemically with theadsorbed precursor, forming a monolayer of a desired material. Theself-limiting nature of the chemical reaction on the surface can provideprecise control of film thickness and large-area uniformity of thedeposited layer. Moreover, the non-directional adsorption of precursoronto exposed surfaces provides for uniform deposition of material ontosurfaces having different orientations relative to chamber 110.

ALD system 100 includes a reaction chamber 110, which is connected tosources 150, 160, 170, 180, and 190 via a manifold 130. Sources 150,160, 170, 180, and 190 are connected to manifold 130 via supply lines151, 161, 171, 181, and 191, respectively. Valves 152, 162, 172, 182,and 192 regulate the flow of gases from sources 150, 160, 170, 180, and190, respectively. Sources 150 and 180 contain a first and secondprecursor, respectively, while sources 160 and 190 include a firstreagent and second reagent, respectively. Source 170 contains a carriergas, which is constantly flowed through chamber 110 during thedeposition process transporting precursors and reagents to substrate 20,while transporting reaction byproducts away from the substrate.Precursors and reagents are introduced into chamber 110 by mixing withthe carrier gas in manifold 130. Gases are exhausted from chamber 110via an exit port 145. A pump 140 exhausts gases from chamber 110 via anexit port 145. Pump 140 is connected to exit port 145 via a tube 146.

ALD system 100 includes a temperature controller 195, which controls thetemperature of chamber 110. During deposition, temperature controller195 elevates the temperature of substrate 101 above room temperature. Ingeneral, the substrate temperature should be sufficiently high tofacilitate a rapid reaction between precursors and reagents, but shouldnot damage the substrate. In some embodiments, the substrate temperaturecan be about 500° C. or less (e.g., about 400° C. or less, about 300° C.or less, about 200° C. or less, about 150° C. or less, about 125° C. orless, about 100° C. or less).

Typically, the substrate temperature should not vary significantlybetween different portions of substrate 20. Large temperature variationscan cause variations in the reaction rate between the precursors andreagents at different portions of the substrate, which can causevariations in the thickness and/or morphology of the deposited layers.In some embodiments, the temperature between different portions of thedeposition surfaces can vary by about 40° C. or less (e.g., about 30° C.or less, about 20° C. or less, about 10° or less, about 5° C. or less).

Deposition process parameters are controlled and synchronized by anelectronic controller 199. Electronic controller 199 is in communicationwith temperature controller 195; pump 140; and valves 152, 162, 172,182, and 192. Electronic controller 199 also includes a user interface,from which an operator can set deposition process parameters, monitorthe deposition process, and otherwise interact with system 100.

Referring to FIG. 2B, the ALD process is started (1010) when system 100introduces the first precursor from source 150 into chamber 110 bymixing it with carrier gas from source 170 (1020). A monolayer of thefirst precursor is adsorbed onto surfaces 21, 22 and 102 of substrate20, and residual precursor is purged from chamber 110 by the continuousflow of carrier gas through the chamber (1030). Next, the systemintroduces a first reagent from source 160 into chamber 110 via manifold130 (1040). The first reagent reacts with the monolayer of the firstprecursor, forming a monolayer of the first material. As for the firstprecursor, the flow of carrier gas purges residual reagent from thechamber (1050). Steps 1020 through 1060 are repeated until the layer ofthe first material reaches a desired thickness (1060).

In embodiments where the films are a single layer of material, theprocess ceases once the layer of first material reaches the desiredthickness (1070). However, where the deposited film is a multilayerfilm, the system can introduce a second precursor into chamber 110through manifold 130 (1080). A monolayer of the second precursor isadsorbed onto the exposed surfaces of the deposited layer of firstmaterial and carrier gas purges the chamber of residual precursor(1090). The system then introduces the second reagent from source 180into chamber 110 via manifold 130. The second reagent reacts with themonolayer of the second precursor, forming a monolayer of the secondmaterial (1100). Flow of carrier gas through the chamber purges residualreagent (1110). Steps 1080 through 1110 are repeated until the layer ofthe second material reaches a desired thickness (1120).

Additional layers of the first and second materials are deposited byrepeating steps 1020 through 1130. Once the desired number of layers isformed, the process terminates (1140), and the coated substrate isremoved from chamber 110.

Although the precursor is introduced into the chamber before the reagentduring each cycle in the process described above, in other examples thereagent can be introduced before the precursor. The order in which theprecursor and reagent are introduced can be selected based on theirinteractions with the exposed surfaces. For example, where the bondingenergy between the precursor and the surface is higher than the bondingenergy between the reagent and the surface, the precursor can beintroduced before the reagent. Alternatively, if the binding energy ofthe reagent is higher, the reagent can be introduced before theprecursor.

The thickness of each monolayer generally depends on a number offactors. For example, the thickness of each monolayer can depend on thetype of material being deposited. Materials composed of larger moleculesmay result in thicker monolayers compared to materials composed ofsmaller molecules.

The temperature of the substrate can also affect the monolayerthickness. For example, for some precursors, a higher temperate canreduce adsorption of a precursor onto a surface during a depositioncycle, resulting in a thinner monolayer than would be formed if thesubstrate temperature were lower.

The type or precursor and type of reagent, as well as the precursor andreagent dosing can also affect monolayer thickness. In some embodiments,monolayers of a material can be deposited with a particular precursor,but with different reagents, resulting in different monolayer thicknessfor each combination. Similarly, monolayers of a material formed fromdifferent precursors can result in different monolayer thickness for thedifferent precursors.

Examples of other factors which may affect monolayer thickness includepurge duration, residence time of the precursor at the coated surface,pressure in the reactor, physical geometry of the reactor, and possibleeffects from the byproducts on the deposited material. An example ofwhere the byproducts affect the film thickness are where a byproductetches the deposited material. For example, HCl is a byproduct whendepositing TiO₂ using a TiCl₄ precursor and water as a reagent. HCl canetch the deposited TiO₂ before it is exhausted. Etching will reduce thethickness of the deposited monolayer, and can result in a varyingmonolayer thickness across the substrate if certain portions of thesubstrate are exposed to HCl longer than other portions (e.g., portionsof the substrate closer to the exhaust may be exposed to byproductslonger than portions of the substrate further from the exhaust).

Typically, monolayer thickness is between about 0.1 nm and about fivenm. For example, the thickness of one or more of the depositedmonolayers can be about 0.2 nm or more (e.g., about 0.3 nm or more,about 0.5 nm or more). In some embodiments, the thickness of one or moreof the deposited monolayers can be about three nm or less (e.g., abouttwo nm, about one run or less, about 0.8 nm or less, about 0.5 nm orless).

The average deposited monolayer thickness may be determined bydepositing a preset number of monolayers on a substrate to provide alayer of a material. Subsequently, the thickness of the deposited layeris measured (e.g., by ellipsometry, electron microscopy, or some othermethod). The average deposited monolayer thickness can then bedetermined as the measured layer thickness divided by the number ofdeposition cycles. The average deposited monolayer thickness maycorrespond to a theoretical monolayer thickness. The theoreticalmonolayer thickness refers to a characteristic dimension of a moleculecomposing the monolayer, which can be calculated from the material'sbulk density and the molecules molecular weight. For example, anestimate of the monolayer thickness for SiO₂ is ˜0.37 um. The thicknessis estimated as the cube root of a formula unit of amorphous SiO₂ withdensity of 2.0 g.cm⁻³.

In some embodiments, average deposited monolayer thickness cancorrespond to a fraction of a theoretical monolayer thickness (e.g.,about 0.2 of the theoretical monolayer thickness, about 0.3 of thetheoretical monolayer thickness, about 0.4 of the theoretical monolayerthickness, about 0.5 of the theoretical monolayer thickness, about 0.6of the theoretical monolayer thickness, about 0.7 of the theoreticalmonolayer thickness, about 0.8 of the theoretical monolayer thickness,about 0.9 of the theoretical monolayer thickness). Alternatively, theaverage deposited monolayer thickness can correspond to more than onetheoretical monolayer thickness up to about 30 times the theoreticalmonolayer thickness (e.g., about twice or more than the theoreticalmonolayer thickness, about three time or more than the theoreticalmonolayer thickness, about five times or more than the theoreticalmonolayer thickness, about eight times or more than the theoreticalmonolayer thickness, about 10 times or more than the theoreticalmonolayer thickness, about 20 times or more than the theoreticalmonolayer thickness).

During the deposition process, the pressure in chamber 110 can bemaintained at substantially constant pressure, or can vary. Controllingthe flow rate of carrier gas through the chamber generally controls thepressure. In general, the pressure should be sufficiently high to allowthe precursor to saturate the surface with chemisorbed species, thereagent to react completely with the surface species left by theprecursor and leave behind reactive sites for the next cycle of theprecursor. If the chamber pressure is too low, which may occur if thedosing of precursor and/or reagent is too low, and/or if the pump rateis too high, the surfaces may not be saturated by the precursors and thereactions may not be self limited. This can result in an uneventhickness in the deposited layers. Furthermore, the chamber pressureshould not be so high as to hinder the removal of the reaction productsgenerated by the reaction of the precursor and reagent. Residualbyproducts may interfere with the saturation of the surface when thenext dose of precursor is introduced into the chamber. In someembodiments, the chamber pressure is maintained between about 0.01 Torrand about 100 Torr (e.g., between about 0.1 Torr and about 20 Torr,between about 0.5 Torr and 10 Torr, such as about 1 Torr).

Generally, the amount of precursor and/or reagent introduced during eachcycle can be selected according to the size of the chamber, the area ofthe exposed substrate surfaces, and/or the chamber pressure. The amountof precursor and/or reagent introduced during each cycle can bedetermined empirically.

The amount of precursor and/or reagent introduced during each cycle canbe controlled by the timing of the opening and closing of valves 152,162, 182, and 192. The amount of precursor or reagent introducedcorresponds to the amount of time each valve is open each cycle. Thevalves should open for sufficiently long to introduce enough precursorto provide adequate monolayer coverage of the substrate surfaces.Similarly, the amount of reagent introduced during each cycle should besufficient to react with substantially all precursor deposited on theexposed surfaces. Introducing more precursor and/or reagent than isnecessary can extend the cycle time and/or waste precursor and/orreagent. In some embodiments, the precursor dose corresponds to openingthe appropriate valve for between about 0.1 seconds and about fiveseconds each cycle (e.g., about 0.2 seconds or more, about 0.3 secondsor more, about 0.4 seconds or more, about 0.5 seconds or more, about 0.6seconds or more, about 0.8 seconds or more, about one second or more).Similarly, the reagent dose can correspond to opening the appropriatevalve for between about 0.1 seconds and about five seconds each cycle(e.g., about 0.2 seconds or more, about 0.3 seconds or more, about 0.4seconds or more, about 0.5 seconds or more, about 0.6 seconds or more,about 0.8 seconds or more, about one second or more)

The time between precursor and reagent doses corresponds to the purge.The duration of each purge should be sufficiently long to removeresidual precursor or reagent from the chamber, but if it is longer thanthis it can increase the cycle time without benefit. The duration ofdifferent purges in each cycle can be the same or can vary. In someembodiments, the duration of a purge is about 0.1 seconds or more (e.g.,about 0.2 seconds or more, about 0.3 seconds or more, about 0.4 secondsor more, about 0.5 seconds or more, about 0.6 seconds or more, about 0.8seconds or more, about one second or more, about 1.5 seconds or more,about two seconds or more). Generally, the duration of a purge is about10 seconds or less (e.g., about eight seconds or less, about fiveseconds or less, about four seconds or less, about three seconds orless).

The time between introducing successive doses of precursor correspondsto the cycle time. The cycle time can be the same or different forcycles depositing monolayers of different materials. Moreover, the cycletime can be the same or different for cycles depositing monolayers ofthe same material, but using different precursors and/or differentreagents. In some embodiments, the cycle time can be about 20 seconds orless (e.g., about 15 seconds or less, about 12 seconds or less, about 10seconds or less, about 8 seconds or less, about 7 seconds or less, about6 seconds or less, about 5 seconds or less, about 4 seconds or less,about 3 seconds or less). Reducing the cycle time can reduce the time ofthe deposition process.

The precursors are generally selected to be compatible with the ALDprocess, and to provide the desired deposition materials upon reactionwith a reagent. In addition, the precursors and materials should becompatible with the material on which they are deposited (e.g., with thesubstrate material or the material forming the previously depositedlayer). Examples of precursors include chlorides (e.g., metalchlorides), such as TiCl₄, SiCl₄, SiH₂Cl₂, TaCl₃, HfCl₄, InCl₃ andAlCl₃. In some embodiments, organic compounds can be used as a precursor(e.g., Ti-ethaOxide, Ta-ethaOxide, Nb-ethaOxide). Another example of anorganic compound precursor is (CH₃)₃Al.

The reagents are also generally selected to be compatible with the ALDprocess, and are selected based on the chemistry of the precursor andmaterial. For example, where the material is an oxide, the reagent canbe an oxidizing agent. Examples of suitable oxidizing agents includewater, hydrogen peroxide, oxygen, ozone, (CH₃)₃Al, and various alcohols(e.g., Ethyl alcohol CH₃OH). Water, for example, is a suitable reagentfor oxidizing precursors such as TiCl₄ to obtain TiO₂, AlCl₃ to obtainAl₂O₃, and Ta-ethaoxide to obtain Ta₂O₅, Nb-ethaoxide to obtain Nb₂O₅,HfCl₄ to obtain HfO₂, ZrCl₄ to obtain ZrO₂, and InCl₃ to obtain In₂O₃.In each case, HCl is produced as a byproduct. In some embodiments,(CH₃)₃Al can be used to oxidize silanol to provide SiO₂.

Referring to FIG. 3, as discussed previously, the ALD process forms amultilayer film on edge surface 101 of substrate 20 in addition tomultilayer films 11 and 12 on surfaces 21 and 22, respectively. Due tothe nature of the ALD process, multilayer film 101 has the samecomposition and thickness as multilayer films 11 and 12, and iscontiguous with multilayer films 11 and 12. Moreover, each layer inmultilayer film 101 is contiguous with corresponding layers inmultilayer films 11 and 12. One such layer, layer 303, is shown in FIG.3. Layer 303 has the same composition and thickness as a correspondinglayer 301 in multilayer film 11 and a layer 302 in multilayer film 12.

In some embodiments, ALD can be used to substantially coat all surfacesof a substrate, encapsulating the substrate. This can be performed byexposing some of surface area of a substrate during an initial ALD run,and coating the remaining surface area in a second ALD run in which theorientation of the substrate in the chamber is varied to exposepreviously covered surface area. Optionally, surfaces coated in theearlier ALD run can be covered in the second run so that substantiallythe same amount of material is deposited on each. Alternatively, surfacearea not coated during the initial ALD run can be sealed using someother coating method. Encapsulating the substrate may be advantageouswhere the substrate material is susceptible to environmental damageand/or the materials forming the films are particularly resistant toenvironmental hazards.

While certain embodiments have been described, other embodiments arepossible.

As an example, while the preparation of IR filter films using ALD hasbeen described, ALD can be used to form other types of films, such as,for example, antireflection films, UV cut-off filters, narrow-bandfilters, DWDM filters, phase compensators, high reflection mirrors,and/or waveguide layers.

As another example, while films having a certain number of layers havebeen described, more generally, a film can have one or more (e.g., two,three, four, five, six, seven, eight, nine, 10, 11, 12, 13, 14, 15)layers. Typically, the number of layers of a multilayer film is selectedbased on the desired optical properties of the film. In some embodiments(e.g., where a multilayer film includes materials having differentthermo-mechanical properties (e.g., different coefficients of thermalexpansion), many layered films may experience greater mechanical stressthan comparable films with fewer layers if subjected to thermal cycling.In some embodiments, a multilayer film may include more than 15 layers(e.g., about 20 layers or more, about 30 layers or more, about 40 layersor more, about 50 layers or more).

While the range of layer thickness in multilayer films 11 and 12 arebetween about 20 nm and 1,000 nm, ALD can be used to deposit film layersthat are thicker or thinner than these values. Layers can be as thin asa single monolayer (e.g., about 0.3 nm to about 2 mn) up to severalthousand nanometers thick (e.g., about 2,000 nm or more, about 3,000 nmor more, about 5,000 nm or more). For example, in some embodiments, thethickness of one or more layers can be substantially less than opticalwavelengths (e.g., substantially less than 200 mn). For example, certainlayers can have a thickness of about 20 nm or less (e.g., about 15 nm orless, about 10 nm or less, about eight run or less, about five nm orless, about two nm or less). In some embodiments, the thickness of alayer can correspond to about 20 monolayers of material or less (e.g.,about 15 monolayers or less, about 10 monolayers or less, about eightmonolayers or less, about five monolayers or less, three monolayers orless, two monolayers, one monolayer), where monolayer thickness refersto the theoretical monolayer thickness discussed previously. Where thethickness of layers in a film are substantially less than opticalwavelengths, the optical properties of the film will be an average ofthe optical properties (e.g., refractive index) of the materialscomposing the film. Films that include layers of materials that aresubstantially less than optical wavelengths are referred to asnanolaminates. In some embodiments, one or more portions of a film canbe nanolaminates. The nanolaminate portions can function like a layerwith a homogeneous index of refraction that is an effective average ofthe indices of refraction of the materials forming the nanolaminate. Insome embodiments, nanolaminates can be used to form graded indexportions in a multilayer film. Examples of nanolaminate portions includeportions composed of SiO₂ monolayers and TiO₂ monolayers, or SiO₂monolayers and Ta₂O₃ monolayers.

Furthermore, while multilayer films 11 and 12 are each composed oflayers of two different materials, in general, films may include layersof more than two different dielectric materials. For example, while allthe high index layers in the described embodiments are formed from thesame material, in general, the high index layers may be formed from thesame or different materials. Similarly, the layers of the low indexmaterials may be formed from the same or different materials. Ingeneral, the number of different material layers in a multilayer filmmay vary as desired.

Furthermore, while the monolayers forming multilayer films 11 and 12 areeach formed from a single dielectric material, in some embodiments, thecomposition of deposited layer can include more than one material. Forexample, by simultaneously introducing more than one precursor intochamber 110, a monolayer of two or more different materials can beformed. The composition of each monolayer in a layer can be varied totailor the refractive index profile of a film.

While films 11 and 12 are continuous over surfaces 21 and 22, in someembodiments, a film on a surface prepared using ALD may be discontinuous(e.g., patterned). Patterning may be performed during or after the ALDprocess. In embodiments where patterning is performed during ALD,portions of the substrate may be treated with a material to which theprecursors and/or reagents do not adhere. No material is deposited inthese portions, while the ALD process deposits layers of material in theuntreated portions. For example, a hydrophobic material, such as aTeflon spray, could be coated onto portions of a surface to reduce wateradsorption onto the surface. Alternatively, or additionally, portions ofa substrate surface may be masked with a material that is removed afterdeposition, removing the portions of film deposited thereon.

Films can be patterned after their deposition using techniques such asphotolithography. For example, an optical filter can be coated with aresist, which is subsequently patterned and etched to expose portions ofthe film. Etching the exposed portions and subsequent removal ofresidual resist results in a patterned film.

Although substrate 10 is an optical flat composed of glass, in general,the composition and shape of a substrate can vary. In general, thesubstrate can be formed from any material compatible with the depositedmaterials, precursors, reagents, and the deposition conditions. Suitablesubstrate materials may include a glass (e.g., borosilicate glass,quartz, soda-lime glass, glass-ceramic), metals (e.g., aluminum,stainless steel, nickel, copper), semiconductors (e.g., silicon,germanium), and/or polymers, such as thermoset polymers andthermoplastic polymers. Examples of polymers include polycarbonate,polyester, polypropylene, acrylic, liquid crystal polymer,polyethylterephthalate, polyamide, polyvinylchloride, and polyethylene.

The substrate may include materials that are sensitive to elevatedtemperatures, and may be damaged if exposed to elevated temperatures. Insuch situations, the substrate temperature should not be elevated totemperature that would damage the substrate during the depositionprocess. In some embodiments, substrate material may be unstable fortemperatures of about 150° C. or more (e.g., about 170° C. or more,about 200° C. or more, about 300° C. or more, about 400° C. or more,about 500° C. or more). For example, a substrate material may undergoundesirable physical and/or chemical changes above a certaintemperature. An example of an undesirable physical change is a phasechange. A liquid crystal polymer substrate may become isotropic above acertain temperature, for example. Some substrate materials (e.g., somepolymers) may undergo a glass transition above a certain temperature.For example, the substrate may include a material that has a glasstransition temperature of about 150° C. or more (e.g., about 200° C. ormore, about 300° C. or more, about 400° C. or more, about 500° C. ormore). An example of a chemical change is oxidation of a substratematerial (e.g., oxidation of a copper substrate).

The substrate material can have similar thermomechanical properties toone or more of the materials used to form the film(s). For example, acoefficient of thermal expansion (CTE) of the substrate material(s) canbe similar to a CTE of one or more of the materials used to form thefilm(s). In some embodiments, the CTE of a substrate material may bewithin about 10% or less (e.g., about 8% or less, about 5% or less) ofthe CTE of a material used to form the film(s) over a range oftemperatures over which the substrate is cycled during formation of thefilm(s) (e.g., from about 0° C. to about 300° C.). Matching thethermomechanical properties of materials in the substrate and films canreduce mechanical stress in the films that may accompany thermalcycling, which could otherwise result in cracking or other damage of thefilm(s).

In some embodiments, the substrate may be an optical element or aportion of an optical element. Optical elements include refractiveelements (e.g., lenses), diffractive elements (e.g., diffractionsgratings), reflectors (e.g., mirrors), and light emitting elements(e.g., light emitting diodes, lasers).

In some embodiments, the substrate surfaces that are coated using ALDcan be substantially planar, such as surfaces 21 and 22 of substrate 10.As used herein, a substantially planar surface has a radius of curvatureof 100 meters or more. Alternatively, the coated surfaces may be curved.A curved surface has a radius of curvature of less than 100 meters. Insome embodiments, a surface can be a structured surface. Structuredsurfaces refer to surfaces having discontinuities in the surface normal.Structured surfaces can have portions that are planar and/or portionsthat are curved. An example of a substrate with a curved surface is alens, such as lens 401 in FIG. 4. Curved surfaces 411 and 421 of lens401 are coated with films 410 and 420, respectively, using ALD. Films410 and 420 conform to surfaces 411 and 421, having a uniform thicknessacross each surface. Films 410 and 420 may include a single layer ormultiple layers of differing composition. In embodiments where films 410and 420 are multilayer films, each layer in the multilayer films canhave a uniform thickness across the film. Films 410 and 420 can be thesame or different. For example, both films can form an optical filter,similar to films 11 and 12 discussed previously. In an alternativeexample, film 10 can be an optical filter, while film 420 can be anantireflection film. In embodiments where the films are identical, theycan be formed simultaneously by exposing both surfaces 411 and 421during the ALD process.

Generally, the curvature of the surfaces coated using ALD may vary. Insome embodiments, a substrate can have a modestly curved surface, andcan have a relatively large radius of curvature, such as about 1 meteror more (e.g., about 2 meters or more, about 3 meters or more, about 5meters or more, about 10 meters or more, about 20 meters or more).Examples of substrate surface with low curvature include some lenses,such as certain lenses used in eyeglasses. Alternatively, in some cases,a substrate surface can have high curvature, and can have a relativelysmall radius of curvature, such as about 10 cm or less (e.g., about 8 cmor less, about 5 cm or less, about 3 cm or less, about 2 cm or less,about 1 cm or less, about 0.5 cm or less, about 0.1 cm or less).Examples of substrate surface with high curvature include variouslenses, such as ball lenses.

In some embodiments, the substrate can include one or more structuredsurface that is coated with a film using ALD. Referring to FIG. 5, anexample of a structured surface is a surface 520 of a Fresnel lens 501.ALD can be used to deposit a film 510 (e.g., a single layer or multilayer film) on slopes 521 and drafts 522 of surface 520. The conformalnature of the ALD process results in film 510 having substantiallyuniform thickness on both slopes 521 and drafts 522. In someembodiments, film 510 is an antireflection film, which can reduce (e.g.,eliminate) ghosting effects that may otherwise be experienced during useof the lens.

Other examples of structured surfaces that may be coated using ALDinclude grating structures, such as ruled gratings and relief gratings,cylindrical surfaces, such as the surface of an optical fiber or aninner surface of a hollow waveguide (e.g., having a circular, square orrectangular cross section). A further example is a cleaved surface of anoptical fiber. For example, some telecommunications applications utilizedesign schemes in which a cleaved fiber is positioned very close to alens or an optical component. Coating an AR film onto a cleaved surfaceusing ALD can reduce reflections at the surface. Multiple cleavedsurfaces can be coated in a single ALD run.

Optical components formed using the methods disclosed herein can be usedin a variety of optical systems. Referring to FIG. 6, in someembodiments, an IR filter 610 formed using ALD techniques is used in animaging system 600. Imaging system includes lenses 620 and 630 whichimage light propagating relative to axis 660 admitted through anaperture 640 onto a detector 650 (e.g., a charge coupled device (CCD) orcomplementary metal oxide semiconductor (CMOS) detector) at an imageplane. IR filter 610 is positioned between lens 620 and detector 650. IRfilter 610 includes multilayer films 611 and 612, and reduces (e.g.,substantially eliminates) the amount of IR light admitted throughaperture 640 that impinges on detector 650. For example, IR filter canreduce the amount of light at a block wavelength by about 20% or more(e.g., about 50% or more, about 80% or more, about 90% or more, about95% or more). In some embodiments, IR filter 610 has a transmissionspectrum similar to the spectrum shown in FIG. 1C.

In some embodiments, ALD may be used to integrate optical components inan optical system. For example, discrete IR filter 610 in imaging system600 can be replaced with a filter coated directly onto one or moresurfaces of the lenses in an imaging system. For example, referring toFIG. 7, an imaging system 700 includes a pair of lenses 720 and 730,which image light propagating relative to axis 760 admitted through anaperture 740 onto a detector 750. An optical filter 710 includesmultilayer films 713, 714, 711, and 712 deposited on surfaces 721, 722,731, and 732 of lenses 720 and 730, respectively. Like IR filter 610shown in FIG. 6, optical filter 710 reduces (e.g., substantiallyeliminates) the amount of IR light admitted through aperture 740 thatimpinges on detector 750.

In a further embodiment, FIG. 8 shows an imaging system 800 including anIR filter 810, which is deposited on a single surface 821 of a lens 820.Imaging system 800 also includes a second lens 830, a detector 850, andan aperture 840. Lenses 820 and 830 image light admitted throughaperture 840 onto detector 850. Surface 821 corresponds to the lenssurface where the divergence of imaged rays is smallest. In other words,a maximum difference in the propagating direction of imaged rays is lessthan a maximum difference in the propagation direction of imaged rays atother surfaces of lenses 720 and 730. Accordingly, the maximum blueshift associated with the band edge of the filter is less when thefilter is located on surface 810 than it would be if located on othersurfaces in imaging system 800.

Ray divergence is illustrated by rays 860 and 870, which originate froma common source point and are imaged to a common point 851 on detector850. The propagation angles of rays 860 and 870 with respect to anoptical axis 899 of imaging system 800 are φ₁ and φ₂, respectively. Thedivergence of the rays is the difference between φ₁ and φ₂. In someembodiments, rays of imaged light have a maximum divergence of about 20degrees or less at IR filter 810 (e.g., about 15 degrees or less, about10 degrees or less, about 8 degrees or less). Accordingly, the blueshift experienced by the system's marginal rays compared to rayspropagating along axis 899 can be about 20 nm or less (e.g., about 15 nmor less, about 12 nm or less, about 10 nm or less).

In another embodiment, FIG. 9 shows an imaging system 900 including anIR filter 910, which is deposited on a surface 951 of a detector 950(e.g., a CCD or CMOS detector). Imaging system 900 also includes a lens920, a second lens 930, and an aperture 940. Lenses 920 and 930 imagelight admitted through aperture 940 onto detector 950.

Imaging systems, such as those discussed previously, may be used inelectronic devices, such as digital cameras and digital camcorders. Insome embodiments, the imaging systems may be used in digital cameras incellular telephones.

The following examples are illustrative and not intended as limiting.

EXAMPLES Example I

An optical filter was formed by depositing multilayer films on oppositesides of a BK7 optical flat (100 mm diameter), which was obtained fromAbrisa (Santa Paula, Calif.). The optical flat was cleaned by removinginsoluble organic contaminants with a H₂O:H₂O₂:NH₄OH solution, andremoving ionic and heavy metal atomic contaminants using a H₂O:H₂O₂:HClsolution. The high index material was TiO₂ and the low index materialwas Al₂O₃. The precursor for the high index material was Ti-ethaoxide,99.999% grade purity, obtained from Sigma-Aldrich (St. Louis, Mo.). Theprecursor for the low index material was (CH₃)₃Al, also 99.999% gradepurity, obtained from Sigma-Aldrich (St. Louis, Mo.). For bothmaterials, the reagent was deionized water, which was provided using awater deionizer obtained from Allied Water Technologies (Danbury,Conn.).

To deposit the multilayer films, the optical flat was placed in a P400AALD reaction chamber, obtained from Planar Systems, Inc. (Beaverton,Oreg.). Air was purged from the chamber. Nitrogen was flowed through thechamber, maintaining the chamber pressure at about 1 Torr. The chambertemperature was set to 170° C. and left for about seven hours for thesubstrate to thermally equilibrate. Once thermal equilibrium wasreached, an initial pulse of water, vapor was introduced into thechamber by opening the valve to the water supply for 0.7 seconds. Afterthe valve to the water supply was closed, the chamber was purged by thenitrogen flow for three seconds. Next, the valve to the (CH₃)₃Al wasopened for 0.8 seconds, introducing (CH₃)₃Al into the chamber. Thechamber was again allowed to purge by the nitrogen flow for 1.5 secondsbefore another dose of water vapor was introduced. Alternating doses ofwater vapor (0.7 seconds) and (CH₃)₃Al (0.8 seconds) were introducedbetween purges, resulting in a layer of Al₂O₃ being formed on theexposed surfaces of the substrate. Total cycle time was seven seconds.This cycle was repeated 95 times, resulting in Al₂O₃ layer having athickness of 9.56 nm.

After depositing the Al₂O₃ layer, water vapor was introduced into thechamber in a two second pulse. This was followed by a two second purge,a one second pulse of Ti-ethaoxide, and another two second purge. Thiscycle was repeated 172 times, resulting in a 6.48 nm thick layer of TiO₂being formed on the Al₂O₃ layer.

Additional layers of Al₂O₃ and TiO₂ were deposited using the stepsoutlined above to multilayer films on the exposed substrate surfaces.The thickness of each layer, and of deposition cycles used to depositeach layer are summarized in Table I. TABLE I Al₂O₃ TiO₂ Layers LayersLayer Thickness No. of Layer Thickness No. of No. (nm) Cycles No. (nm)Cycles 1 9.56 95 2 6.48 172 3 55.63 551 4 20.71 551 5 49.71 492 6 18.88502 7 39.36 390 8 96.86 2576 9 127.25 1259 10 79.18 2106 11 119.8 118612 76.72 2041 13 117.67 1164 14 75.87 2018 15 117.01 1158 16 75.67 201317 116.98 1158 18 75.7 2014 19 117.03 1158 20 76.93 2046 21 119.59 118322 82.97 2207 23 105.81 1047 24 3.22 86 25 29.9 296 26 105.85 2815 2722.3 221 28 7.1 189 29 127.76 1264 30 99.21 2639 31 51.26 507 32 18.26486 33 24.61 244 34 47.07 1252 35 4.4 44 36 17.41 463 37 128.82 1275 3882.89 2205 39 137.68 1362 40 92.65 2464 41 8.64 86 42 10.28 273 43154.44 1528 44 24.33 647 45 3.62 36 46 76.72 2041 47 153.64 1520 48105.56 2808 49 156.42 1548 50 105.05 2794 51 156.48 1549 52 105.32 280153 155.2 1536 54 104.77 2787 55 154.23 1526 56 98.52 2620 57 129.08 127758 14.32 381 59 13.1 130 60 49.28 1311 61 69.86 691 62

Referring to FIG. 10, the performance of the optical filter wasinvestigated using a Lamba 14 UV/V is spectrometer, obtained fromPerkin-Elmer (Wellesley, Mass.). The transmission spectrum of theoptical filter was measured at 0° and 30° incidence. At 0°, the passband extended from about 380 nm to about 680 nm. Transmission at thesewavelengths out 90%. The optical filter substantially blocked light atwavelengths from about 690 nm to about 1,100 nm. The band edge at 680 nmshifted by about 20 nm to about 650 nm for dent at 30°. TABLE II Al₂O₃TiO₂ Layers Layers Layer Thickness No. of Layer Thickness No. of No.(nm) Cycles No. (nm) Cycles 1 41.51 411 2 8.47 221 3 29.73 294 4 89.252329 5 127.44 1261 6 79.52 2075 7 119.16 1179 8 77.71 2028 9 117.56 116310 79.33 2070 11 125.63 1243 12 11.66 304 13 21.64 214 14 15.41 402 15129.94 1286 16 78.52 2049 17 117.08 1159 18 76.5 1995 19 117.2 1160 2077.56 2024 21 120.61 1194 22 82.66 2157 23 138.9 1374 24 91.7 2393 256.11 60 26 10.19 266 27 146.04 1445 28 99.41 2594 29 33.44 331 30 16.07419 31 24.47 242 32 87.07 2272 33 129.63 1283 34 86.99 2270 35 142.961415 36 102.91 2686 37 37.76 374 38 1.19 31 39 112.79 1116 40 101.712654 41 133.7 1323 42 1.82 47 43 19.92 197 44 102.18 2667 45 147.2 145746 98.22 2563 47 33.3 330 48 6.1 159 49 138.14 1367 50 12.82 335 5135.08 347 52 105.85 2762 53 147.48 1459 54 97.71 2550 55 7.44 74 56 5.74150 57 147.74 1462 58 97.34 2540 59 122.3 1210 60 10.55 275 61 15.77 15662 51.44 1342 63 68.84 681

Example II

An optical filter is formed using the method described in Example I. Thehigh index material is TiO₂ and the low index material is Al₂O₃. Theprecursor for the high index material is Ti-ethaoxide and the precursorfor the low index material is TMA. For both materials, the reagent isdeionized water.

Initially, a 307.7 nm thick Al₂O₃ buffer layer is deposited. This layeris formed by 3045 ALD cycles. The thickness of each additional layer,and number of deposition cycles used to deposit each layer aresummarized in Table I. The cycle times are the same as those describedin Example I.

Referring to FIG. 11, the performance of the optical filter isinvestigated using a spectrometer. The transmission spectrum of theoptical filter is measured at 0’. At 0° incidence, the pass band extendsfrom about 390 nm to about 650 nm. Transmission at these wavelengths isbetween about 92% and about 94%. The optical filter substantially blockslight at wavelengths from about 670 nm to about 1,100 nm.

Other embodiments are in the following claims.

1. An optical system, comprising: a lens for imaging light from anobject to an image plane; and an optical filter comprising a pluralityof layers positioned relative to the lens to reduce an amount of focusedlight of a wavelength λ by about 20 percent or more at the image planerelative to an identical optical system without the optical filter,wherein one of the layers is disposed on a first surface of the lens. 2.The optical system of claim 1, wherein the first surface has a radius ofcurvature of about two meters or less.
 3. The optical system of claim 1,wherein the image plane is about 5 cm or less from the lens.
 4. Theoptical system of claim 1, wherein the image plane is about 1 cm or lessfrom the lens.
 5. The optical system of claim 1, wherein the image planeis about 0.5 cm or less from the lens.
 6. The optical system of claim 1,further comprising a detector positioned at the image plane.
 7. Theoptical system of claim 6, wherein the detector is a charge coupleddevice array or complementary metal oxide semiconductor array.
 8. Theoptical system of claim 6, wherein the optical filter is disposed on asurface of the detector.
 9. The optical system of claim 1, wherein theplurality of layers comprise a plurality of dielectric layers.
 10. Theoptical system of claim 1, wherein alternating layers of the pluralityof layers have different refractive indices.
 11. The optical system ofclaim 1, wherein the plurality of layers comprises a layer disposed on asecond surface of the lens opposite the first surface.
 12. The opticalsystem of claim 1, wherein λ is about 650 nm or more.
 13. The opticalsystem of claim 1, wherein λ is between about 650 nm and 1,100 nm. 14.The optical system of claim 1, wherein the optical filter reducesfocused light of wavelength λ by about 50 percent or more at the imageplane.
 15. The optical system of claim 1, wherein the optical filterreduces focused light of wavelength λ by about 80 percent or more at theimage plane.
 16. The optical system of claim 1, wherein the opticalfilter reduces focused light of wavelength λ by about 90 percent or moreat the image plane.
 17. The optical system of claim 1, wherein theoptical filter reduces focused light of wavelength λ by about 95 percentor more at the image plane.
 18. The optical system of claim 1, furthercomprising a second lens for imaging light from the object to the imageplane, wherein the one of the layers of the optical filter is disposedon a surface of the second lens.
 19. The optical system of claim 1,wherein rays of imaged light have a maximum divergence of about 20degrees or less at the first surface.
 20. The optical system of claim 1,wherein rays of imaged light have a maximum divergence of about 15degrees or less at the first surface.
 21. The optical system of claim 1,wherein rays of imaged light have a maximum divergence of about 10degrees or less at the first surface.
 22. The optical system of claim 1,wherein the optical filter is positioned between the lens and the imageplane.
 23. A digital camera comprising the optical system of claim 1.24. A cell phone comprising the digital camera of claim
 23. 25. Anoptical system, comprising an optical filter positioned relative a lensand an image plane, wherein the optical filter comprises: a substratehaving first and second surfaces, wherein the first surface is oppositethe second surface; and a first and second multilayer film disposed onthe first and second surfaces, respectively, wherein the firstmultilayer film is identical to the second multilayer film.